Absorption, emission and excitation spectra of two water-free LiI crystals prepared from different origins were observed at liquid nitrogen temperature. Emission band with a peak at 3.40 eV is excited above the energy of the fundamental absorption edge, and excitation spectra of this band for both crystals are same with each other. Excitation spectrum of this band shows not only a sharp dip reflecting an exciton absorption band, but also a phonon side-band of the exciton.